The present invention relates to methods for controlling insects. In particular, it relates to control by the application of certain novel substituted benzenes.
The present invention relates to methods for controlling insects. In particular, it relates to control by the application of certain novel substituted benzenes. More particularly, it pertains to 1,4-disubstituted benzene compounds and compositions containing the same which are useful for controlling insects in agricultural crops. Even more particularly, this invention relates 1,4-disubstituted benzene compounds and compositions and their uses as insecticides against a variety of insects, including larvae, such as tobacco budworm.
It has now been found that certain substituted benzenes, particularly 1,4-disubstituted benzenes, and their agriculturally acceptable salts, are effective as insecticides. These benzenes may be represented by the following formula I: 
in which:
A is hydrogen; aryl; alkylheterocyclyl; alkenylaminopolycyclyl; alkenylaminoheterocyclyl; alkylaminopolycyclyl; carbonylaminopolycyclyl; and Formula III, where Formula III is
xe2x80x83xe2x80x94(CH2)nxe2x80x94Uxe2x80x94R2xe2x80x83xe2x80x83III
where
n is 0 or 1;
U is xe2x80x94CH2xe2x80x94, xe2x80x94Oxe2x80x94CH2xe2x80x94, oxygen, sulfur, sulfonyl, alkyl, oxyalkyloxy, alkenylamino, cabonylamino and xe2x80x94NR5, where R5 is hydrogen, hydroxy, alkyl, haloalkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;
R2 is aryl; alkylpolycyclyl; heterocyclyl; polycyclyl; 1-R3; 1-R4; and 2-R4, where:
R3 is 
where
J, L, and W are independently hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, aminoalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, aryloxy, and heterocyclyl;
R4 is 
where
X, Y, and Z are independently hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, aryloxy, and heterocyclyl;
B and D are independently hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyaminoalkyl, 2-(Formula III), 3-(Formula III), 5-(Formula III), and 6-(Formula III), where Formula III, n, U, R2, R3, R4, R5, J, L, W, X, Y, and Z are as defined above;
R is xe2x80x94Txe2x80x94(CH2)mxe2x80x94R1, xe2x80x94N(R6)(R7) or heterocyclyl;
T is xe2x80x94CH2xe2x80x94, carbonyl, oxygen, nitrogen, and sulfur;
m is 0, 1, 2, 3, or 4;
R1 is xe2x80x94N(R8)(R9); alkyl; aryl; xe2x80x94C(O)N(R12)(R13); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; xe2x80x94N(O)(R14)(R15); xe2x80x94P(O)(R14)(R15); xe2x80x94P(S)(R14)(R15); alkylamino, where the cyclohexyl, aryl and heterocyclyl moieties may be optionally substituted with halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, alkylamino; where
R6, R7, R8, R9, R12, R13, R14 and R15 are independently hydrogen, alkyl, alkoxy, alkylthio, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and xe2x80x94(CH2)pxe2x80x94N(R16)(R17), where
p is 1 or 2; and
R16 and R17 are independently hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl.
The present invention is also directed to a composition containing an insecticidally effective amount of a compound of Formula I in admixture with at least one agriculturally acceptable extender or adjuvant, wherein A, B, D, and R are as defined above.
In addition, the present invention relates to a method of controlling insects that comprises applying to locus on crops, such as cotton, vegetables, fruits, where control is desired an insecticidally effective amount of a the above composition.
In one aspect of the present invention, certain substituted benzenes, particularly 1,4-disubstituted benzenes, and the agriculturally acceptable salts thereof, have now been found to be effective as insecticides. These benzenes may be represented by the following formula I: 
in which:
A is selected from the group consisting of hydrogen; aryl; alkylheterocyclyl; alkenylaminopolycyclyl; alkenylaminoheterocyclyl; alkylaminopolycyclyl; carbonylaminopolycyclyl; where the aryl, heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and Formula III, where Formula III is
xe2x80x94(CH2)nxe2x80x94Uxe2x80x94R2xe2x80x83xe2x80x83III
wherein
n is 0 or 1;
U is selected from the group consisting of xe2x80x94CH2xe2x80x94, xe2x80x94Oxe2x80x94CH2xe2x80x94, oxygen, sulfur, sulfonyl, alkyl, oxyalkyloxy, alkenylamino, cabonylamino and xe2x80x94NR5, where R5 is selected from the group consisting of hydrogen, hydroxy, alkyl, haloalkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;
R2 is selected from aryl; alkylpolycyclyl; heterocyclyl; polycyclyl; where the aryl, heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; 1-R3; 1-R4; and 2-R4, wherein:
R3 is 
where
J, L, and W are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, aminoalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, aryloxy, and heterocyclyl, where the aryl and heterocyclyl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;
R4 is 
where
X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, aryloxy, and heterocyclyl, where the phenyl, aryl, and heterocyclyl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;
B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyaminoalkyl, 2-(Formula III), 3-(Formula III), 5-(Formula III), and 6-(Formula III), wherein Formula III, n, U, R2, R3, R4, R5, J, L, W, X, Y, and Z are as defined above;
R is xe2x80x94Txe2x80x94(CH2)mxe2x80x94R1, xe2x80x94N(R6)(R7) or heterocyclyl, where
the heterocyclyl moiety may be optionally substituted with halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, alkylaza, arylcarbonyl, benzyl, allyl, propargyl, alkylamino; where the aryl moiety may be optionally substituted with halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl
T is selected from the group consisting of xe2x80x94CH2xe2x80x94, carbonyl, oxygen, nitrogen, and sulfur;
m is 0, 1, 2, 3, or 4;
R1 is selected from the group consisting of xe2x80x94N(R8)(R9); alkyl; aryl; xe2x80x94C(O)N(R12)(R13); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; xe2x80x94N(O)(R14)(R15); xe2x80x94P(O)(R14)(R15); xe2x80x94P(S)(R14)(R15); alkylamino, where the cycloalkyl, aryl and heterocyclyl moieties may be optionally substituted with halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, alkylamino; where
R6, R7, R8, R9, R12, R13, R14 and R15 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkylthio, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and xe2x80x94(CH2)pxe2x80x94N(R16)(R17), where
p is 1 or 2;
R16 and R17 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl.
Agriculturally acceptable salts of the 1,4-disubstituted benzenes include, but are not limited to, for example, the salts of hydrochloric acid, sulfonic acid, ethanesulfonic acid, trifluoroacetic acid, methylbenzenesulfonic acid, phosphoric acid, gluconic, acid, and pamoic acid.
Some preferred compounds are those in which
A is selected from the group consisting of hydrogen; alkylaminopolycyclyl; carbonylaminopolycyclyl; where the polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and Formula III, where Formula III is
xe2x80x94(CH2)nxe2x80x94Uxe2x80x94R2xe2x80x83xe2x80x83III
wherein
n is 0 or 1;
U is selected from the group consisting of xe2x80x94CH2xe2x80x94, oxygen, and xe2x80x94NR5, where R5 is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;
R2 is selected from aryl, alkylpolycyclyl; heterocyclyl; polycyclyl; where the aryl, heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and 1-R3, wherein R3 is: 
where
J, L, and W are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, and aryloxy, where the aryl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;
B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyaminoalkyl;
R is xe2x80x94Txe2x80x94(CH2)mxe2x80x94R1, where
T is selected from the group consisting of xe2x80x94CH2xe2x80x94, oxygen, nitrogen, and sulfur;
m is 1, 2, 3, or 4;
R1 is xe2x80x94N(R8)(R9), where
R8 and R9 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and xe2x80x94(CH2)pxe2x80x94N(R16)(R17), where
p is 1 or 2;
R16 and R17 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl;
and the corresponding agriculturally acceptable salts thereof.
Some particularly preferred compounds are those in which
A is hydrogen or Formula III, where Formula III is
xe2x80x94(CH2)nxe2x80x94Uxe2x80x94R2xe2x80x83xe2x80x83III
wherein
n is 0 or 1;
U is selected from the group consisting of xe2x80x94CH2xe2x80x94, oxygen, and xe2x80x94NR5, where R5 is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;
R2 is selected from heterocyclyl; polycyclyl; where the heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and 1-R3, wherein R3 is: 
where
J, L, and W are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, ammo, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, and aryloxy, where the aryl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;
B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyamninoalkyl;
T is oxygen or nitrogen
m is 2, 3, or 4;
R1 is xe2x80x94N(R8)(R9), where
R8 and R9 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and xe2x80x94(CH2)pxe2x80x94N(R16)(R17), where
p is 1 or 2;
R16 and R17 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl.
Some more particularly preferred compounds are those in which A is Formula III, where Formula III is
xe2x80x94(CH2)nxe2x80x94Uxe2x80x94R2xe2x80x83xe2x80x83III
wherein
n is 1;
U is oxygen or xe2x80x94NR5, where R5 is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;
R2 is 1-R3, wherein R3 is: 
where
J, L, and W are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, and aryloxy, where the aryl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;
B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyaminoalkyl;
T is oxygen or nitrogen
m is 2;
R1 is xe2x80x94N(R8)(R9), where
R8 and R9 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and xe2x80x94(CH2)pxe2x80x94N(R16)(R17), where
p is 1 or 2;
R16 and R17 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl;
Some yet even more particularly preferred compounds are those in which
U is oxygen or xe2x80x94NR5, where R5 is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;
R2 is 1-R3, wherein R3 is: 
where
J, L, and W are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, and aryloxy, where the aryl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;
B and D are independently selected from hydrogen, halogen, and alkoxy;
T is oxygen;
R1 is xe2x80x94N(R8)(R9); where
R8 and R9 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and xe2x80x94(CH2)pxe2x80x94N(R16)(R17), where
p is 1 or 2;
R16 and R17 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl;
Some still yet even more particularly preferred compounds are those in which U is oxygen or xe2x80x94NR5, where R5 is hydrogen; R2 is 1-R3, wherein R3 is: 
where
J, L, and W are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, and aryloxy, where the aryl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;
B and D are hydrogen;
R1 is xe2x80x94N(R8)(R9); where R8 and R9 are alkyl.
In another aspect, the present invention is directed to certain novel 1,4-disubstituted benzenes per se and agriculturally acceptable salts thereof falling within the scope of formula I above. These compounds include, for example, the following novel 1,4-disubstituted benzenes: 
in which:
A is Formula III, where Formula III is
xe2x80x94(CH2)nxe2x80x94Uxe2x80x94R2xe2x80x83xe2x80x83III
wherein
n is 1;
U is oxygen;
R2 is 1-R3; wherein:
R3 is 
where
J is 2-chloro or 2-fluoro, L is 3-chloro or 5-fluoro, and W is hydrogen or 4-chloro,
B and D are hydrogen;
R is xe2x80x94Txe2x80x94(CH2)mxe2x80x94R1, where
T is oxygen;
m is 2;
R1 is xe2x80x94N(R8)(R9), where R8 and R9 are ethyl.
Additional preferred compounds are those in which A is selected from the group consisting of hydrogen; alkylaminopolycyclyl; and carbonylaminopolycyclyl; where the polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and Formula III, where Formula III is
xe2x80x94(CH2)nxe2x80x94Uxe2x80x94R2xe2x80x83xe2x80x83III
wherein
n is 0 or 1;
U is selected from the group consisting of xe2x80x94CH2xe2x80x94, oxygen, alkyl, oxyalkyloxy, alkenylamino, cabonylamino and xe2x80x94NR5, where R5 is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;
R2 is selected from aryl; alkylpolycyclyl; heterocyclyl; polycyclyl; where the aryl, heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and 1-R4, wherein R4 is 
where
X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;
B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, and alkoxyaminoalkyl;
R is xe2x80x94Txe2x80x94(CH2)mxe2x80x94R1 or heterocyclyl; where
the heterocyclyl moiety may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl, propargyl;
T is selected from the group consisting of xe2x80x94CH2xe2x80x94, oxygen, nitrogen, and sulfur;
m is 1, 2, 3, or 4;
R1 is selected from the group consisting of xe2x80x94N(R8)(R9); alkyl; aryl; xe2x80x94C(O)N(R12)(R13); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; and xe2x80x94N(O)(R14)(R15), where the aryl and heterocyclyl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl; where
R8, R9, R12, R13, R14 and R15 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and xe2x80x94(CH2)pxe2x80x94N(R16)(R17), where
p is 1 or 2;
R16 and R17 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl;
and the corresponding agriculturally acceptable salts thereof.
Additional particularly preferred compounds are those in which A is hydrogen or Formula III, where Formula III is
xe2x80x94(CH2)nxe2x80x94Uxe2x80x94R2xe2x80x83xe2x80x83III
wherein
n is 0 or 1;
U is selected from the group consisting of xe2x80x94CH2xe2x80x94, oxygen, and xe2x80x94NR5, where R5 is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;
R2 is selected from alkylpolycyclyl; heterocyclyl; polycyclyl; where the heterocyclyl and polycyclyl moieties are optionally substituted with one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and R4, wherein R4 is 
where
X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;
B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, and alkoxyaminoalkyl;
R is xe2x80x94Txe2x80x94(CH2)mxe2x80x94R1 or heterocyclyl; where
the heterocyclyl moiety may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl, propargyl;
T is selected from the group consisting of oxygen, nitrogen, and sulfur;
m is 1, 2, 3, or 4;
R1 is selected from the group consisting of xe2x80x94N(R8)(R9); alkyl; aryl; xe2x80x94C(O)N(R12)(R13); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; and xe2x80x94N(O)(R14)(R15), where the aryl and heterocyclyl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl; where
R8, R9, R10, R13, R14 and R15 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and xe2x80x94(CH2)pxe2x80x94N(R16)(R17), where
p is 1 or 2;
R16 and R17 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl;
and the corresponding agriculturally acceptable salts thereof.
Additional more particularly preferred compounds are those in which A is Formula III, where Formula III is
xe2x80x94(CH2)nxe2x80x94Uxe2x80x94R2xe2x80x83xe2x80x83III
wherein
n is 1;
U is oxygen or xe2x80x94NR5, where R5 is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;
R2 is 1-R4, wherein R4 is 
where
X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;
B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, and alkoxyaminoalkyl;
R is xe2x80x94Txe2x80x94(CH2)mxe2x80x94R1 or heterocyclyl; where
the heterocyclyl moiety may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl, propargyl;
T is oxygen or nitrogen;
m is 1, 2, 3, or 4;
R1 is selected from the group consisting of xe2x80x94N(R8)(R9); alkyl; aryl; xe2x80x94C(O)N(R12)(R13); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; and xe2x80x94N(O)(R14)(R15), where the aryl and heterocyclyl moieties may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl; where
R8, R9, R12, R13, R14 and R15 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and xe2x80x94(CH2)pxe2x80x94N(R16)(R17), where
p is 1 or 2;
R16 and R17 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl;
and the corresponding agriculturally acceptable salts thereof.
Additional yet even more particularly preferred compounds are those in which A is Formula III, where Formula III is
xe2x80x94(CH2)nxe2x80x94Uxe2x80x94R2xe2x80x83xe2x80x83III
wherein
U is oxygen or xe2x80x94NR5, where R5 is hydrogen;
R2 is 1-R4, wherein R4 is 
where
X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;
B and D are independently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, and alkoxyaminoalkyl;
R is xe2x80x94Txe2x80x94(CH2)mxe2x80x94R1 or heterocyclyl; where
the heterocyclyl moiety may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl, propargyl;
T is oxygen or nitrogen;
m is 2;
R1 is xe2x80x94N(R8)(R9) or xe2x80x94N(O)(R14)(R15), where R8, R9, R14, and R15 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and xe2x80x94(CH2)pxe2x80x94N(R16)(R17), where
p is 1 or 2;
R16 and R17 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl;
and the corresponding agriculturally acceptable salts thereof.
Additional still yet even more particularly preferred compounds are those in which
A is Formula III, where Formula III is
xe2x80x83xe2x80x94(CH2)nxe2x80x94Uxe2x80x94R2xe2x80x83xe2x80x83III
wherein
U is O or xe2x80x94NR5, where R5 is hydrogen;
R2 is selected from 1-R4, wherein R4 is 
where
X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;
B and D are hydrogen;
the heterocyclyl is a piperazinyl moiety, where the the piperazinyl moiety may be optionally substituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl, propargyl;
T is oxygen;
R1 is xe2x80x94N(R8)(R9) or xe2x80x94N(O)(R14)(R15), where R8, R9, R14, and R15 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, and carbonylamino;
and the corresponding agriculturally acceptable salts thereof.
Further preferred compounds are those in which
A is Formula III, where Formula III is
xe2x80x94(CH2)nxe2x80x94Uxe2x80x94R2xe2x80x83xe2x80x83III
wherein
U is O;
R2 is selected from 1-R4, wherein R4 is 
where
X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;
R1 is xe2x80x94N(R8)(R9) or xe2x80x94N(O)(R14)(R15), where R8, R9, R14 and R15 are alkyl;
and the corresponding agriculturally acceptable salts thereof.
In addition to those compounds set forth above, the present invention is also directed to certain novel 1,4-disubstituted benzenes per se and agriculturally acceptable salts thereof falling within the scope of formula I above. These compounds include, for example, the following novel 1,4-disubstituted benzenes: 
in which:
A is Formula III, where Formula III is
xe2x80x94(CH2)nxe2x80x94Uxe2x80x94R2xe2x80x83xe2x80x83III
wherein
n is 1;
U is oxygen;
R2 is 1-R4; wherein:
R4 is 
where
X is 4-chloro or 5-chloro, Y is 6-chloro or 6-bromo, and Z is hydrogen;
B and D are hydrogen;
R is xe2x80x94Txe2x80x94(CH2)mxe2x80x94R1 or a piperazinyl moiety; where
the piperazinyl moiety is substituted with 4-ethyl;
T is oxygen;
m is 2;
R1 is xe2x80x94N(R8)(R9) or xe2x80x94N(O)(R14)(R15), where R8, R9, R14 and R15 are ethyl;
and the agriculturally acceptable salts thereof, preferably the hydrochloride salts.
In another aspect, the present invention is directed to a composition containing an insecticidally effective amount of a compound of Formula I, including, without limitation, those compounds disclosed above as being preferred, particularly preferred, and per se novel, in admixture with at least one agriculturally acceptable extender or adjuvant, wherein A, B, D, and R are as defined above.
In another aspect, the present invention relates to a method of controlling insects that comprises applying to locus on crops, such as cotton, vegetables, fruits, where control is desired an insecticidally effective amount of the above compositions.
Certain intermediates or the present invention are novel. These include compounds of formula XII: 
wherein:
A is xe2x80x94(CH2)nxe2x80x94Uxe2x80x94R2 
wherein
n is 0 or 1;
U is xe2x80x94C(O)xe2x80x94, xe2x80x94CH2xe2x80x94, oxygen, or xe2x80x94NR5, where R5 is selected from the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;
R2 is selected from hydrogen, halo, hydroxy, and 1-R4, wherein:
R4 is 
where
X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;
R is xe2x80x94Txe2x80x94(CH2)mxe2x80x94R1, where
T is selected from the group consisting of oxygen, nitrogen, and sulfur;
m is 0, 1, 2, 3, or 4;
R1 is hydrogen, halo, alkyl, or xe2x80x94N(R8)(R9); where R8 and R9 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and xe2x80x94(CH2)pxe2x80x94N(R16)(R17), where
p is 1 or 2;
R16 and R17 are independently selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl.
Some preferred intermediates are those in which n is 1; U is oxygen; R2 is 1-R4, wherein:
R4 is 
where
X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;
T is oxygen or sulfur;
m is 2; and
R1 is halo.
Some particularly preferred intermediates are those in which n is 1; U is xe2x80x94CH2xe2x80x94; R2 is 1-R4, wherein:
R4 is 
where
X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;
T is oxygen;
m is 0; and
R1 is hydrogen or alkyl.
Additional preferred intermediates are those in which n is 0; U is xe2x80x94C(O) or xe2x80x94CH2xe2x80x94; R2 is hydrogen, halo or hydroxy; T is oxygen; m is 2; and R1 is xe2x80x94N(R8)(R9), where R8 and R9 are alkyl.
Additional novel intermediates are compounds of formula UU: 
where
X, Y, and Z are independently selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and aryl moieties may be optionally substituted with halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy; T is selected from the group consisting of oxygen, nitrogen, and sulfur; and R18 is alkyl.
For the purposes of this invention, as regards to the above substituents, the following definitions apply:
The terms xe2x80x9calkylxe2x80x9d and xe2x80x9calkoxyxe2x80x9d, alone or as part of a larger moiety, include chains of 1 to 14 carbon atoms, preferably straight or branched alkyls of 1 to 6 carbon atoms; while xe2x80x9chalogenxe2x80x9d or xe2x80x9chaloxe2x80x9d, alone or as part of a larger moiety, includes chlorine, bromine, fluorine, and iodine atoms. The terms xe2x80x9calkenylxe2x80x9d or xe2x80x9calkynylxe2x80x9d, used alone or as part of a larger moiety, includes straight or branched chains of at least two carbon atoms containing at least one carbonxe2x80x94carbon double or triple bond, preferably upto 12 carbon atoms, more preferably, up to ten carbon atoms, most preferably up to seven c carbon atoms. The term xe2x80x9ccycloalkylxe2x80x9d includes rings of three to twelve carbon atoms, preferably rings of three to six carbon atoms. The terms xe2x80x9chaloalkylxe2x80x9d and xe2x80x9chaloalkoxyxe2x80x9d, alone or as part of a larger moiety, include straight or branched chain alkyls of 1 to 14 carbon atoms, preferably lower straight or branched chain alkyls of 1 to 6 carbon atoms, wherein one or more hydrogen atoms have been replaced with halogen atoms, as, for example, trifluoromethyl or 2,2,2-trifluoroethoxy, respectively. xe2x80x9cArylxe2x80x9d refers to an aromatic ring structure, including fused rings, having 5 to 10 carbon atoms. xe2x80x9cHeterocyclylxe2x80x9d refers to an aromatic ring structure, including fused rings, having at least one nitrogen, sulfur or oxygen atom. xe2x80x9cAminoxe2x80x9d refers to compounds of nitrogen that may be considered derived from ammonia and includes primary, secondary and tertiary amines wherein one or more of the hydrogen atoms is replaced with alkyl groups. xe2x80x9cTHFxe2x80x9d refers to tetrahydrofuran, xe2x80x9cDMFxe2x80x9d refers to N,N-dimethylformamide, xe2x80x9cDPADxe2x80x9d refers to 1,1xe2x80x2-(azodicarbonyl)dipiperidine, and xe2x80x9cA.T.xe2x80x9d refers to ambient temperature.
The compounds of the present invention were prepared by methods generally known to those skilled in the art. Many of the compounds of the present invention in which R1 is naphthyl were prepared in the manner shown in Schema 1. In Schema 1, a 4-hydroxy-benzaldehyde (SM1) was reacted with the appropriately substituted alkyl chloride hydrochloride salt (SM2) in a solvent, for example, DMF or THF, at 0xc2x0 C. to ambient temperature in the presence of a base, for example, potassium carbonate, to yield the appropriately substituted alkoxy benzaldehyde (BB). The appropriately substituted benzaldehyde (BB) was then reduced in a solvent, for example methanol, with a reducing agent, for example, lithium aluminum hydride, sodium borohydride, or triacetoxyborohydride, to yield the appropriately substituted phenyl alkoxy alcohol (CC). The appropriately substituted phenyl alkoxy alcohol (CC) can also be prepared by reacting the appropriately substituted alkyl chloride hydrochloride salt (SM2) with either the appropriately substituted acid (SM3) or phenyl alcohol (SM4) in a solvent in the presence of a reducing agent as set forth above. The appropriately substituted phenyl alkoxy alcohol (CC) can then be reacted with either p-toluene sulfonyl chloride (SM5) and a base, for example triethylamine, in a solvent to form the appropriately substituted phenyl alkylthio- or alkoxysulfonyl toluene (DD) or sulfonyl chloride in a solvent to form the appropriately substituted phenylalkylthio or phenylalkoxy chloride hydrochloride (EE).
If necessary, the naphthyl ring can be prepared at this time. In general, the naphthyl ring was prepared via the formation of the appropriate naphthol. The preparation of the naphthol begins by reacting: 1) the appropriately substituted benzaldehyde (SM6) with either sodium hydride and 3-(triphenylphosphino)propanoate hydrochloride in THF and N-N-dimethylsulfoxide (DMF) or with succinic acid, disodium salt and acetic anhydride to form the appropriately substituted phenylbutenoic acid (FF); 2) the appropriately substituted phenyl iodide (SM7) with but-3-ynol, a base, for example, triethylamine, copper iodide and a palladium phosphine complex to yield the appropriately substituted phenylbutynol (GG); 3) the appropriately substituted phenylcarbonylpropanoic acid (SM8) with zinc and mercury (II) chloride in water to form the appropriately substituted phenylbutanoic acid (HH), which can also be preprepared by hydrogenating the appropriately substituted phenylbutenoic acid (FF) or phenylbutynol (GG) in alcohol with palladium on carbon followed by treatment with chromium oxide and sulfuric acid; 4) the appropriately substituted 2-(diethylaminocarbonyl)benzene (SM9) with n-butyllithium followed by prop-2-enylbromide and a dimethylthio-copper chloride complex to yield the appropriately substituted 2-(diethylaminocarbonyl)-3-prop-2-enylbenzene (JJ); or 5) the appropriately substituted benzene (SM10) with oxolan-2-one and aluminium chloride at elevated temperature to form the appropriately substituted trihydronaphthalen-1-one (KK). The trihydronaphthalen-1-one (KK) can also be prepared by reacting the appropriately substituted phenylbutanoic acid (HH) with an acid, for example polyphosphoric acid, or reacting the appropriately substituted 2-(diethylaminocarbonyl)-3-prop-2-enylbenzene (JJ) with methyllithium. The appropriately substituted trihydronaphthalen-1-one (KK) is then reacted with bromine in a solvent, for example methylene chloride, to form the the appropriately substituted 2-bromo-trihydronaphthalen-1-one (LL). The appropriately substituted 2-bromo-trihydronaphthalen-1-one (LL) is then reduced with a reducing agent and lithiumbromide in a solvent, for example, DMF, in the manner described above to form the appropriately substituted naphthol (MM), which is commercially available when (MM) is 4-chloronaphthol. The appropriately substituted naphthol (MM) was then reacted with either the appropriately substituted benzaldehyde (BB), alcohol (CC), toluene (DD), or hydrochloride (EE) to form the targeted 1-substitutedalkylthio or alkoxy-4-((substituted naphth-1-yl)oxyalkyl)benzene (I), for example, (2-(4-(((4-chloronaphthyl)methoxy)methyl)phenoxy)ethyl)diethylamine.
Additional substituents can be added to the naphthol ring by reacting a 6-aminonaphth-1-ol (SM11) with toluene sulfonyl chloride in the manner disclosed above to yield the 6-amino-1-(methylphenylsulfonyloxy)naphthalene (NN). The 6-amino-1-(methylphenylsulfonyloxy)naphthalene (NN) was then reacted with t-butyl nitrite in a solvent, for example at 0xc2x0 C. followed by a copper (II) halide, for example, copper (II) chloride, to yield the appropriate 6-halo-1-(methylphenylsulfonyloxy)naphthalene (PP). The 6-amino-1-(methylphenylsulfonyloxy)naphthalene (NN) was also reacted with an excess of a copper (II) halide, for example, copper (II) chloride, in a solvent followed by t-butylnitrite in the manner disclosed above to form the appropriate 5,6-dihalo-1 -(methylphenylsulfonyloxy)naphthalene (QQ). The appropriately substituted naphthalene (QQ) or (PP) can then reacted with a base, for example, potassium hydroxide, and an alcohol, for example, ethanol, in a mixture of a solvent, for example, THF, and water to yield the appropriately substituted naphthol (RR), for example 5,6-dichloronaphthol. When the naphthol was a 5,6-dihalonaphthol (RR) it was reacted with either the appropriately substituted benzaldehyde (BB), alcohol (CC), toluene (DD), or hydrochloride (EE) and a borane-pyridine complex under acidic conditions, or a base, for example, sodium hydride or triethylamine, in a solvent, for example DMF, or a phosphine complex, for example n-butylphosphine, and DPAD in a solvent, for example, THF, to form the targeted 1-substitutedalkylthio or alkoxy-4-((5,6-substituted naphth-1-yl)oxyalkyl)benzene (Ia), for example, (2-(4-((5,6-dichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine.
A halo substituent, for example chloro, can be added to the 4-position of naphthol ring at this time by reacting the appropriately substituted naphthol (MM) or (RR) with a sulfuryl halide, for example, sulfuryl chloride, in a solvent to yield the appropriately substituted 4-halonaphthol (SS). The appropriately substituted 4-halonaphthol (SS) can be reacted either the appropriately substituted benzaldehyde (BB), alcohol (CC), toluene (DD), or hydrochloride (EE) in the manner described above to form the targeted 1-substitutedalkylthio or alkoxy-4-((5,6-substituted naphth-1-yl)oxyalkyl)benzene (Ib), for example, (2-(4-((4,6-dichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine.
As depicted in Schema 2, compounds of the present invention wherein U is nitrogen and n is 1 were prepared by reacting the appropriately substituted benzaldehyde (BB) with the appropriately substituted 1-aminonaphthalene (SM12), for example, 1-amino-4-chloronaphthalene, under acidic conditions to form the appropriately substituted 1-aza-1-naphthyl-2-phenylethene (TT), which was then reduced with a reducing agent in the manner disclosed above to yield the targeted targeted 1-substituted -4-((substituted naphth-1-yl)aminoalkyl)benzene (IV), for example, (2-(4-(((4-chloronaphthyl)amino)methyl)phenoxy)-ethyl)diethylamine.
As depicted in Schema 3, compounds of the present invention wherein U is xe2x80x94CH2xe2x80x94 and n is 1 were prepared by reacting the appropriately substituted 1-aminonaphthalene (SM12) with the appropriately substituted 4-methylthio-, 4-methoxy-, or 4-methylamino-1-vinylbenzene (SM13) with t-butylnitrite, in a solvent, for example, acetonitrile, in the presence of palladium acetate to form the appropriately substituted 2-(4-methylthio-, 4-methoxy-, or 4-methylaminophenyl)vinylnaphthalene (UU). The vinylnaphthalene was then hydrogenated in a solvent, for example, ethanol, with a palladium on carbon to form the appropriately substituted 2-(4-methylthio-, 4-methoxy-, or 4-methylaminophenyl)ethylnaphthalene (WW). The ethylnaphthalene (WW) was then reacted in solvent, for example methylene chloride, with boron tribromide to form the appropriately substituted 2-(4-thio-, 4-hydroxy-, or 4-aminophenyl)ethylnaphthalene (XX). The ethylnaphthalene (XX) was in turn reacted with the appropriately substituted alkyl chloride hydrochloride salt (SM2) and an excess of a base, for example, potassium carbonate, in solvent, for example, DMF, to form the targeted 1-substituted -4-((substituted naphth-1-yl)ethyl)benzene (V), for example, (2-(4-(((4-chloronaphthyl)amino)methyl)phenoxy)-ethyl)diethylamine.
Schema 4 depicts another route in which the compounds of the present invention may be prepared. In Schema 4, the appropriately substituted benzaldehyde (SM3) is reacted with a haloalkylbromide, for example, 1-bromo-2-chloromoethane, to yield the appropriately substituted 4-haloalkoxybenzaldehdye (YY), which in turn is reduced with a reducing agent in an alcohol, for example methanol, in the manner described above to form the appropriately substituted 4-haloalkoxyphenylmethan-1-ol (ZZ). The phenylmethan-1-ol (ZZ) was then reacted at 0xc2x0 C. to ambient temperature with the appropriately substituted naphthol or phenol (SM14), a phosphine complex, and DPAD in a solvent in the manner described above to yield the corresponding halo-1-(4-substituted naphthyl- or 4-substituted phenyl)oxy)methyl)phenoxy)alkane (AAA), for example, 2-chloro-1-(4-((4-chloronaphthyloxy)methyl)phenoxy)ethane. The alkane (AAA) was then reacted with the appropriate substituent, for example, cis-2,6-dimethylpiperidine, and a base in acetonitrile to form the corresponding, 1-(substituted alkoxy)-4-((4-substituted naphthyl or phenyl)oxy)methyl)benzene (VI), for example 1-(2-(2,6-dimethylpiperidyl)ethoxy)-4-((4-chloronaphthyloxy)methyl)benzene. At this point, the benzene (VI) can optionally be reacted with 3-chloroperoxybenzoic acid in chloroform at 0 C. to form the corresponding 2-(4-substituted naphthyl or phenyl)oxy)methyl)phenoxy)alkyl)alkanone (VII), for example, amino(2-(4-((5,6-dichloronaphthyloxy)methyl)phenoxy)ethyl)diethyl-1-one.
Schema 5 illustrates yet another route for preparing the compounds of the present invention wherein R1 is a disubstituted amino. In schema 5, the appropriately substituted (4-hydroxyphenyl)methan-1-ol (SM4) was reacted with a bromomethylisocyanate and a reducing agent, for example potassium carbonate, in a solvent, for example, DMF, in the manner disclosed above to form the corresponding (4-(cyanomethoxy)phenyl)methan-1-ol (BBB). The methan-1-ol (BBB) was then reacted with sulfinyl chloride in a solvent, for example, chloroform, at 0xc2x0 C. to form the corresponding 4-(cyanomethoxy)-1-(chloromethyl)benzene (CCC), which was in turn reacted with the appropriately substituted naphthol or phenol (SM14) and a reducing agent, for example, potassium carbonate, in a solvent, for example DMF, in the manner described above to yield the corresponding 1-(((4-substituted naphthyl- or 4-substituted phenyl)oxy)methyl)-4-(cyanomethoxy)benzene (DDD). The 4-(cyanomethoxy)benzene (DDD) was reacted with borane in a solvent, for example, THF, at 0xc2x0 C. to form the appropriately substituted 1-(((4-substituted naphthyl- or 4-substituted phenyl)oxy)methyl)-4-(aminomethoxy)benzene (EEE). The 4-(aminomethoxy)benzene (EEE) was in turn reacted with the appropriate oxoalkyl chloride, for example, acetyl chloride, in a solvent, for example, pyridine or THF, at 0xc2x0 C. to yield the corresponding 1-(((4-substituted naphthyl- or 4-substituted phenyl)oxy)methyl)-4-(oxoalkylaminomethoxy)benzene (FFF). The 4-(oxoalkylaminomethoxy)benzene (FFF) was then reacted with borane in a solvent in the manner described above to yield the targeted 1-(((4-substituted naphthyl- or 4-substituted phenyl)oxy)methyl)-4-(alkylaminomethoxy)benzene (VIII). At this point, additional moieties can be optionally added to the amino group by reacting the 4-(alkylaminomethoxy)benzene (VIII) with the appropriate substituted alkyl, alkoxy, or alkoxyalkyl halide and a base, for example, triethylamine, to yield the target 1-(((4-substituted naphthyl- or 4-substituted phenyl)oxy)methyl)-4-((disubstituted amino)methoxy)benzene (IX). 
The present invention is now described in more detail by reference to the following examples, but it should be understood that the invention is not construed as being limited thereto.